Patent GB-913987-A (GB)
Title: A process for the production of chlorinated phenols with recovery of hydrochloric acid
IPC: C01B7/01
Filed: 1959-01-08
Abstract: <PICT:0913987/IV (b)/1> Technical grade pentachlorophenol having a minimum actual pentachlorophenol content of 85% is produced by chlorinating phenol in the presence, during at least the latter part of the reaction, of from 0.004 to 0.0085 moles of anhydrous aluminium chloride per mole of phenol while maintaining the reaction mass in the liquid state and at a temperature below 130 DEG C. until the freezing-point of the partiallychlorinated liquid has reached 120 DEG C. and thereafter gradually adjusting the reaction temperature above the freezing point of the reaction mass so that the mathematical product of (1) the differential between the reaction mass temperature and its freezing point expressed in degrees centigrade and (2) the chlorination time required to produce a product with a freezing point of 174 DEG C., is from 0 to 60 centigrade-hours.  The chlorination may be carried out in the absence of a catalyst until 1 to 3 atoms, preferably 2.3 atoms, of chlorine have been combined per mole of phenol; and thereafter it is continued in the presence of catalyst. The process may be operated so as to obtain 2,4-dichlorophenol as by-product.  In Example 1, phenol was charged to primary reactor 15 and to secondary reactor 18; and 0.00445 moles of anhydrous aluminium per mole of phenol were added to reactor 15.  Chlorine from cylinder 10 was passed through the reactors.  The temperature of reactor 18 was maintained at 45 DEG C. throughout the chlorination.  The temperature of reactor 15 was maintained at 45 DEG C. until 1 atom of chlorine had combined per mole of phenol.  The temperature in reactor 15 was then increased to 65 DEG C. and held at 65 DEG C. until the freezing-point of the product reached 64 DEG C.  The temperature was then increased continuously but held to within no more than 3 DEG C. above the product freezing-point, resulting in a mathematical product of 6 degree-hours.  The product of reactor 15 had a final freezing-point of 177 DEG C., and comprised 92.6% pentachlorophenol and 5.4% tetrachlorophenol.  The product of reactor 18 consisted of 2-chlorophenol and 4-chlorophenol.  The gases from reactor 18 were passed through trap 21 and thence into tower 22 wherein they were absorbed in water to make 36% hydrochloric acid.  In Example 6, the product from reactor 18 of a previous batch was charged to reactor 15.  This partially -chlorinated phenol contained 28% of combined chlorine.  Phenol was placed in reactor 18.  Anhydrous aluminium chloride was added to both reactors.  The temperature of reactor 18 was held at 70 DEG C. throughout the chlorination.  The temperature in reactor 15 was held at 100 DEG C. until the freezing-point of the product was 95 DEG C.  The temperature was then adjusted sufficiently above the freezing-point of the product to produce a mathematical product of 14 degree-hours.  The reaction was terminated when the product in reactor 15 had a freezing-point of 176 DEG C.; it consisted of 88% pentachlorophenol. The product of reactor 18 comprised primary 2,4-dichlorophenol with lesser amounts of monochlorophenol and trichlorophenol.